US20050009967A1 - Phosphite stabilizers and methods to preparation and polymer composition thereof - Google Patents

Phosphite stabilizers and methods to preparation and polymer composition thereof Download PDF

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US20050009967A1
US20050009967A1 US10/860,706 US86070604A US2005009967A1 US 20050009967 A1 US20050009967 A1 US 20050009967A1 US 86070604 A US86070604 A US 86070604A US 2005009967 A1 US2005009967 A1 US 2005009967A1
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phosphite
group
tert
carbon atoms
composition
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Hayder Zahalka
Carloss Gray
Vaikunth Prabhu
Marshall Moore
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Lanxess Solutions US Inc
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Crompton Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • the present invention generally relates to compositions and stabilizers for polymeric resin compositions, and more particularly to stabilized resin compositions and stabilizer concentrates for resin compositions.
  • Neoalkyl phenyl phosphites are known as stabilizers in the art.
  • U.S. Pat. No. 3,467,733 discloses the preparation of phosphites and diphosphites, such as bis(1,3,2-dioxaphosphorinyl-2-oxy)aryl alkenes and mono-and bis (1,2,3-dioxaphosphorinanyl-2-oxy)benzenes, for use as stabilizers for organic compositions.
  • 3,467,733 further discloses the reaction of a cyclic phosphorohalidite with a hydroxy aromatic compound, subsequently neutralizing the reaction product with a nitrogen containing compound such as ammonia and recovering the desired cyclic phosphite and diphosphite.
  • substitutions (X,Y,Z) on phenol are independently selected from group consisting of —H and alkyl of 1-5 carbon atoms, and sum of the carbon atoms in X, Y, and Z does not exceed 5.
  • U.S. Pat. Nos. 5,618,866 and 5,594,053 which disclose phosphite compositions derived from neodiol chlorophosphite and 2,4-di-substituted phenols using an amine acceptor.
  • U.S. Pat. No. 5,786,497 discloses the preparation of phosphites from phenol with alkyl substitution at 2,4,and 6 position, with the reaction with chlorophosphite derivative being carried out in an excess amine medium (acceptor technology), subsequently followed by the removal of hydrogen chloride by forming amine hydrochloride.
  • composition of matter comprising phosphites derived from 2,4-di-alkyl-phenol and pentaerythritol chlorophosphite and aliphatic polyamines in polyolefins are known in the art, see for example, U.S. Pat. No. 5,514,742.
  • Specific compositions comprising phosphites derived from 2,4,6-tri-alkyl-phenol and neodiol is described in U.S. Pat. No. 5,424,348.
  • Amorphous neodiol based phosphite compositions with polyamine are described in U.S. Pat. Nos. 5,674,927; 5,468,895; and 5,605,947.
  • U.S. Pat. No. 4,305,866 discloses stabilization of polyolefin with a phosphite.
  • the phosphites in the prior art are prepared by a direct method, wherein the phosphite is obtained by the reaction of a neoglycol with PCl 3 in the absence of a catalyst, HCl acceptor and solvent. HCl is liberated in the process to form the phosphite derivative, e.g., triplienylphosphite synthesis from phenol and PCl3.
  • the phosphites in the prior art can also be prepared by another process, a trans-esterification method in which triphenylphosphite is reacted with an alcohol, and the phenol is liberated and distilled.
  • U.S. Pat. No. 5,618,866 discloses yet another process to manufacture phosphite stabilizers, i.e., an acceptor technology, wherein chlorophosphorohalidite is prepared by reacting alcohol or phenol with PCl 3 , and then this is reacted with an alcohol or phenol in presence of an amine catalyst to form the phosphite derivative. Amine hydrochloride salts are then isolated from the product of the intermediate reaction.
  • phosphite stabilizers in the prior art i.e., hindered neoalkyl phosphite compositions as disclosed in U.S. Pat. No. 5,464,889, are obtained in the presence of a solvent and have undesirable odors, which make the handling and processing of the materials unpleasant.
  • a low odor phosphite stabilizer would be an advancement in the art. Applicants have developed a solvent-less process for making neo diol phosphite esters for phosphite stabilizer products with surprisingly low odor levels.
  • neoalkyl aryl phosphite with improved handling properties by eliminating extra steps and elimination of storage/recovery/purification/recycle of intermediates.
  • neoalkyl phenyl phosphite compositions exhibiting improved thermal, hydrolytic stability in polymers. Applicants have found a process to produce phosphites from 2,4-dialkyl or 2,4-di-alkylaryphenol and neodiol based chlorophosphites by direct reaction, for a phosphite product that surprisingly has no odor or low in odor, particularly useful in thermoplastic compositions such as polyolefins.
  • the present invention relates to a process for the preparation of a neo diol phosphite stabilizer by a direct or solvent-less method, comprising the steps of reacting a neoalkyl chlorophosphite with a mono- or di-substituted hydroxylated aromatic compound which is present in excess amount at a temperature of about 40 to about 250° C., removing HCl by applying controlled vacuum or by sweeping the HCl gas under nitrogen or a stream of an inert gas, and finally removing the respective excess of hydroxylated aromatic compound and neo diol phosphite from the reaction mixture under reduced pressure.
  • the present invention further relates to a neo diol phosphite stabilizer prepared by a direct or solvent-less process, wherein the phenol is substituted at the 2- and 4-position with an alkyl or alkylaryl group and the stabilizer is characterized as having a low odor or no odor.
  • the present invention also relates to polymeric compositions comprising a stabilizing effective amount of a low odor or no odor neo diol phosphite stabilizer prepared by a direct or solvent-less process.
  • the present invention further relates to a thermoplastic composition stabilized against degradation, said composition comprising: (a) a thermoplastic resin or mixture thereof; (b) a low odor or no odor neo diol phosphite stabilizer; and (c) a stabilizing effective amount of a stabilizer or a mixture of stabilizers selected from the group consisting of the phenolic antioxidants, the hindered amine light stabilizers, the ultraviolet light stabilizers, the organic phosphorus compounds, the alkaline metal salts of fatty acids, the hydroxylamines, tertiary amine oxides, the 3-arylbenzofuranones, and the thiosynergists.
  • a stabilizer or a mixture of stabilizers selected from the group consisting of the phenolic antioxidants, the hindered amine light stabilizers, the ultraviolet light stabilizers, the organic phosphorus compounds, the alkaline metal salts of fatty acids, the hydroxylamines, tertiary
  • the present invention also pertains to stabilized compositions wherein component (a) is a polyolefin resin or mixture thereof.
  • component (c) comprises: (x) a stabilizing amount of a phenolic antioxidant or mixture thereof; or (y) a stabilizing amount of a phenolic antioxidant or mixture thereof in combination with a stabilizing amount of: (i) an organic phosphorus compound or mixture thereof; or (ii) a hindered amine stabilizer or mixture thereof; or (iii) a thiosynergist or mixture thereof; or (iv) an ultraviolet light absorber or mixture thereof; or (v) a hindered amine stabilizer and an organic phosphorus compound or mixtures thereof; or (vi) a hindered amine stabilizer, a thiosynergist and an organic phosphorus compound or mixtures thereof; or (vii) an ultraviolet light absorber and a hindered amine stabilizer or mixtures thereof; or (vii) an ultraviolet light absorber and an organic phosphorus compound or mixtures thereof; or (ix) an alkaline metal salt of a phenolic antioxidant or mixture thereof; or (y) a stabilizing
  • FIG. 1 is a comparison of the melt flow control observed from chromium-catalyzed high density polyethylene with phosphites both within (Example 17) and outside (Comparative Examples 13 and 14) the scope of the invention;
  • FIG. 2 is a graphical comparison of the color observed from chromium-catalyzed high density polyethylene with phosphites both within (Example 17) and outside (Comparative Examples 13 and 14) the scope of the invention;
  • FIG. 3 is a graphical comparison of the color observed from chromium-catalyzed high density polyethylene with phosphites both within (Example 17) and outside (Comparative Examples 13 and 14) the scope of the invention, when exposed to NOx gases; the color of the chromium-catalyzed polyethylene samples being shown as the yellowness index over the number of days of exposure to the NOx gases;
  • FIG. 4 is a graphical comparison of the thermal aging observed over a twenty day period for a chromium-catalyzed high density polyethylene with phosphites both within (Example 17) and outside (Comparative Examples 13 and 14) the scope of the invention; when placed in an oven at 60° C., the thermal aging of the chromium-catalyzed polyethylene samples being shown as the yellowness index over the number of days in the oven at 60° C.;
  • FIG. 5 is a comparison of the melt flow stability observed from Ziegler Natta-catalyzed linear low density polyethylene with phosphites both within (Example 18) and outside (Comparative Examples 15 and 16) the scope of the invention;
  • FIG. 6 is a graphical comparison of the color observed from Ziegler Natta-catalyzed linear low density polyethylene with phosphites both within (Example 18) and outside (Comparative Examples 15 and 16) the scope of the invention; the color of the Ziegler Natta-catalyzed linear low density polyethylene samples being shown as the yellowness index over the first, third and fifth multipass extrusion;
  • FIG. 7 is a graphical comparison of the gas fading observed from Ziegler Natta-catalyzed linear low density polyethylene with phosphites both within (Example 18) and outside (Comparative Examples 15 and 16) the scope of the invention, when exposed to NOx gases; the gas fading of the Ziegler Natta-catalyzed linear low density polyethylene samples being shown as the yellowness index over the number of hours of exposure to the NOx gases;
  • FIG. 8 is a comparison of the melt flow observed from metallocene-catalyzed linear low density polyethylene with phosphites both within (Example 19) and outside (Comparative Examples 17 and 18) the scope of the invention;
  • FIG. 9 is a graphical comparison of the color observed from metallocene-catalyzed linear low density polyethylene with phosphites both within (Example 19) and outside (Comparative Examples 17 and 18) the scope of the invention; the color of the metallocene-catalyzed linear low density polyethylene samples being shown as the yellowness index over the first, third and fifth multipass extrusion;
  • FIG. 10 is a graphical comparison of the color observed from metallocene-catalyzed linear low density polyethylene with phosphites both within (Example 19) and outside (Comparative Examples 17 and 18) the scope of the invention, when exposed to NOx gases; the color of the metallocene-catalyzed linear low density polyethylene samples being shown as the yellowness index over the number of days of exposure to the NOx gases;
  • FIG. 11 is a is a comparison of the melt flow observed from polypropylene with phosphites both within (Example 20) and outside (Comparative Examples 19 and 20) the scope of the invention;
  • FIG. 12 is a graphical comparison of the color observed from polypropylene with phosphites both within (Example 20) and outside (Comparative Examples 19 and 20) the scope of the invention; the color of the polypropylene samples being shown as the yellowness index over the first, third and fifth multipass extrusion; and,
  • FIG. 13 is a graphical comparison of the in polymer hydrolytic stability of phosphites within and outside the scope of the present invention at 60° C. over a 70 day period at 60° C. relative humidity.
  • Odor is that property of a substance that makes it perceptible to the sense of smell. Specifically, odor is that property that is manifested by a physiological sensation caused by contact of the molecules of a substance with the olfactory nervous system.
  • the present invention relates to thermoplastic and thermoset compositions, and phosphite stabilizers for thermoplastic and thermoset compositions, and more particularly relates to improved phosphite stabilizers being low in odor or free in odor.
  • stabilizing amount or an “effective amount” of the phosphites of the invention is meant when the polymer composition containing the phosphites of the invention shows improved stability in any of its physical or color properties in comparison to an analogous polymer composition which does not include a phosphite of the invention.
  • improved stability is meant improved stabilization against, for example, molecular weight degradation, color degradation, and the like from, for example, melt processing, weathering, and/or long term field exposure to heat, light, and/or other elements.
  • an improved stability is meant one or both of lower initial color or additional resistance to weathering, as measured, for example, by initial yellowness index (YI), or by resistance to yellowing and change in color, when compared to a composition without the stabilizer additive.
  • YI initial yellowness index
  • solvent-less in the process of the presence invention is meant the absence of or without the requirement for a solvent as in the processes of the prior art, i.e., the reaction of a neoglycol chlorophosphite, with substituted phenols using HCl acceptor, e.g., amines, and using inert solvents such as, for example, toluene, heptane, xylene, methylene chloride, chloroform, benzene and the like.
  • Solvent-less herein also refers to the absence of or without the need for a solvent in the reaction as compared to need of solvent as in case of a typical “acceptor technology” route.
  • Other examples of such solvents include hindered alcohols, e.g., isopropyl alcohol, and tert-butylalcohol.
  • the stabilizers of the present invention are selected from the group of 2,4-dialkyl-phenol derived phosphites, having the general formula A: wherein the OX group is hindered by at least one R 1 ; R 1 and R 2 are independently alkyl groups having from 1 to 9 carbon atoms and wherein the R 1 and R 2 alkyl groups have a combined total of carbon atoms of at least 5.
  • R 1 and R 2 are secondary or tertiary branched alkyl groups.
  • R 1 and R 2 are selected from tertiary alkyl groups.
  • the R 1 group and a phenyl group or a substituted phenyl group are positioned at the respective ortho- and para-positions with respect to the OX group.
  • the phosphite stabilizer is a 2,4-dicumylphenol based phosphite structure of the general formula B:
  • R 3 and R 4 are independently alkyl groups of from 1 to 6 carbon atoms. In another embodiment, R 3 and R 4 are independently a straight chain alkyl group.
  • R 5 in one embodiment is hydrogen, a halogen, or an alkyl group of from 1 to 12 carbon atoms.
  • the integer m has a value from 0 to 5.
  • the dicumyl group includes the OX group which is the phosphite portion. Generally, the OX group is hindered by only one alkyl aryl group at the ortho position, with the other ortho position being occupied by hydrogen.
  • X has the following structure (C): wherein R 8 is independently alkyl groups having 1 to 12 carbon atoms; R 6 and R 7 are independently hydrogen, halogen, or an alkyl group of from 1 to 3 carbon atoms. In one embodiment, the R 6 groups are hydrogen. In another embodiment, the alpha-carbon for the ring structure includes at least one hydrogen substituent.
  • the above phosphite entities in one embodiment are formed from 1,3-alkane diols with the beta or 2-position being blocked by alkyl or cyclic alkyl groups.
  • X has the following formulae: Direct/Solvent-less Process to Prepare Phosphite Stabilizers
  • the present invention further relates to a direct/solvent-less process for preparing the foregoing neo diol phosphite stabilizers.
  • the phenol is substituted at 2- and 4-position with an alkyl or alkylaryl group and is used in about 1 to about 30% excess by molar ratio with the removal of HCl gas.
  • excess of unreacted 2,4-di-substituted phenol and neodiol chlorophosphite is removed at the end of the reaction under reduced pressure, to advantageously provide a stabilizer product that has a low odor or no odor.
  • chlorophosphite is added to the substituted phenol in the first about 0.1 to about 4 hours with the temperature of the addition being kept in the range of about 40 to about 80° C.
  • the reaction is held generally for a time period ranging from about 5 to about 20 hours at a reduced pressure ranging from about 1 mm to about 100 mm with the removal of HCl gas or conducted by a sweep of an inert gas, e.g., nitrogen, helium or argon.
  • excess of the unreacted phenol and chlorophosphite may be removed by any conventional process, e.g., distillation process, under reduced pressure and at a temperature range of about 40° C. to about 250° C.
  • the product is then isolated from the reactor, and can be further purified by distillation if liquid or crystallized from an organic solvent and dried.
  • a neoalkyl chlorophosphite is reacted directly with a substituted phenol, e.g., a mono- or di-substituted hydroxylated aromatic compound, with or without the use of catalysts and at a temperature ranging from about 40° C. to about 250° C. under reduced pressure.
  • a substituted phenol e.g., a mono- or di-substituted hydroxylated aromatic compound
  • a catalyst may be used to enhance the reaction rate of the reaction between chlorophosphite intermediate and substituted phenol forming the corresponding phosphite derivative.
  • an amine such as, for example, tri-isopropanolamine, is added to the reaction to improve the hydrolytic stability of the end-product phosphite stabilizer depending on the intended use.
  • catalysts useful in the process of the present invention are those described in EP-A 0,000,757.
  • catalysts of this type include compounds belonging to the group comprising amines or ammonium salts; amides of carboxylic acids or of carbonic acid; non-aromatic N-containing heterocyclic compounds and salts thereof, primary, secondary and tertiary phosphines and salts thereof ;or esters of phosphoric acids and phosphonic acids.
  • the catalysts are selected from the amines and ammonium salts, amides and nitrogen-containing heterocyclic compounds or phosphines containing, as substituents, alkyl; cycloalkyl; aryl, e.g., phenyl; alkaryl, e.g., alkylated phenyl; aralkyl, e.g., benzyl; or alkaralkyl, e.g., alkylated benzyl, groups which preferably contain 1 to about 18 carbon atoms, and preferably 1 to about 12 carbon atoms, and are interrupted, if appropriate, by oxygen or sulfur atoms.
  • Alkyl groups containing 1 to 6 carbon atoms, and cycloalkyl groups, e.g., cyclopentyl and cyclohexyl group may be used.
  • the catalysts to be used in the form of salts are preferably the halides, e.g., chlorides.
  • the salts can also be formed in situ by means of the hydrogen halide formed in the course of the process. Nevertheless, it is advantageous in certain cases to employ the salts themselves as catalysts.
  • the amines and ammonium salts comprise one catalyst group. Examples include primary, secondary and tertiary amine salts.
  • the salts also include the quaternary ammonium salts.
  • catalysts are in the form of secondary amines, e.g., their salts and the quaternary ammonium salts.
  • the catalysts are in the form of alkyl-substituted and cycloalkyl-substituted amines or ammonium salts.
  • catalysts are selected from the group of methylamine, ethylamine, propylamine, n-butylamine, t-butylamine, pentylamine, octylamine, dodecylamine, phenylamine, benzylamine, dimethylamine, diethylamine, methylethylamine, methylbutylamine, methyoctylamine, methylphenylamine, ethylbenzylamine, trimethylamine, triethylamine, tributylamine, octyldimethylamine, dimethylphenylamine, tetramethylamonium, trimethylethylamonium, triethylmethylamonium, tributylmethylamonium, tetrabutyla
  • catalysts are in the form of ammonium salts such as, for example, methylammonium, octylammonium, dimethylammonium, methylcyclohexylammonium, dibenzylammonium, diphenylammonium, trimethylammonium, tributylammonium, tribenzylammonium and triphenylammonium chloride, bromide and iodide.
  • ammonium salts such as, for example, methylammonium, octylammonium, dimethylammonium, methylcyclohexylammonium, dibenzylammonium, diphenylammonium, trimethylammonium, tributylammonium, tribenzylammonium and triphenylammonium chloride, bromide and iodide.
  • the amides of carboxylic acids constitute another group of catalysts. This group also includes the ureas and their bisurea derivatives.
  • the amides can be derived from polyfunctional, preferably monofunctional, carboxylic acids containing, in particular, 1 to 14 carbon atoms.
  • the amides can also be derived from aromatic N-heterocyclic compounds. Cyclic amides, for example epsilon-caprolactam, are also suitable. Examples include formamide, oxamide, dimethylformamide, acetamide, N,N-dimethylkacetamide, picoanilide, benzamide, terephthalamide, and trimallitamide.
  • the preferred catalysts include independently N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone or mixture thereof.
  • the catalyst can be employed in amounts of, for example, about 0.0001 to about 10 mol. % range relative to the reactants.
  • Any HCl gas generated may be pulled from the reaction vessel out by applying low vacuum pressure, e.g., in the range of about 10 to about-140 torr Hg, to just remove the HCl and not the raw materials from the reactor.
  • the HCl gas is removed by sweeping with an inert gas such as dry nitrogen or Argon.
  • an inert gas such as dry nitrogen or Argon.
  • excess of the unreacted phenol and chlorophosphite is removed by distillation process under reduced pressure.
  • excess of the unreacted phenol and chlorophosphite is removed after the reaction is at least 75% complete.
  • the phosphite product is isolated in high yields (90+%) and in high purity (90+%).
  • the phosphites as isolated may be used directly in the liquid form.
  • the phosphite product undergoes an additional distillation step for further purification and use in the solid form by imbibing on microporous resins such as, for example, Accurel® resin (Membrana GmbH).
  • the phosphite product of the invention is used in a stabilizing amount of about 50 ppm to about 5 weight percent, preferably about 0.001 to about 2 weight percent and most preferably from about 0.0025 to about 1 weight percent, based on the total weight of the resin composition.
  • a number of resins may be stabilized by the phosphites of the present invention.
  • the polymers may be any thermoplastic known in the art, such as polyolefin homopolymers and copolymers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals and halide containing polymers.
  • polymers such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS or other impact modified polymers, such as methacrylonitrile and alpha-methylstyrene containing ABS, and polyester/ABS or polycarbonate/ABS and polyester plus some other impact modifier may also be used.
  • Such polymers are available commercially or may be made by means well known in the art.
  • the benzimidazole additive compounds and stabilizer compositions of the invention are particularly useful in thermoplastic polymers, such as polyolefins, polycarbonates, polyesters, polyphenylene ethers and styrenic polymers, due to the extreme temperatures at which thermoplastic polymers are often processed and/or used.
  • Polymers of monoolefins and diolefins for use herein include, but are not limited to, polyethylene ((which optionally can be crosslinked), polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene, or polybutadiene, as well as polymers of cycloolefins, e.g., cyclopentene or norbornene.
  • Mixtures of these polymers for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g., PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (e.g., LDPE/HDPE), may also be used.
  • copolymers of monoolefins and diolefines with each other or with other vinyl monomers such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene, propylene/isobutylene, ethylene/butane-1, propylene/butadiene, isobutylene, isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of such
  • the olefin polymers may be produced by, for example, polymerization of olefins in the presence of Ziegler-Natta catalysts optionally on supports such as, for example, Mg Cl 2 , chronium salts and complexes thereof, silica, silica-alumina and the like.
  • the olefin polmers may also be produced utilizing chromium catalysts or single site catalysts, e.g., metallocene catalysts such as, for example, cyclopentadiene complexes of metals such as Ti and Zr.
  • the polyethylene polmers used herein can contain various comonomers such as, for example, 1-butene, 1-hexene and 1-octene comonomers.
  • the polymer to be stabilized herein is polyethylene and include, but is not limited to, high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
  • Polymers may also include, but are not limited to, styrenic polymers, e.g., polystyrene, poly-(p-methylstyrene), poly-(.alpha.-methylstyrene), copolymers of styrene or .alpha-methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/maleimide, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methylacrylate, mixtures of high impact strength from styrene copolymers and another polymer such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer;
  • Styrenic polymers may additionally or alternatively include graft copolymers of styrene or alpha-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and copolymers thereof, styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or male imide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, sty
  • Nitrile polymers are also useful in the polymer composition of the invention. These include, but are not limited to, homopolymers and copolymers of acrylonitrile and its analogs, such as polymethacrylonitrile, polyacrylonitrile, acrylonitrile/-butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS compositions as referred to above in regard to styrenics.
  • homopolymers and copolymers of acrylonitrile and its analogs such as polymethacrylonitrile, polyacrylonitrile, acrylonitrile/-butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS compositions as referred to above in regard to styrenics.
  • Acrylic acids such as, for example, acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and esters thereof may also be used.
  • Such polymers include, but are not limited to, polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile-type monomer has been replaced by an acrylic acid ester or an acrylic acid amide.
  • Polymers including other acrylic-type monomers such as, for example, acrolein, methacrolein, acrylamide and methacrylamide may also be used.
  • Halogen-containing polymers may also be useful. These include, but are not limited to, resins such as polychloroprene, epichlorohydrin homo- and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinylacetate copolymers, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride isoprene
  • polystyrene resin examples include, but are not limited to, homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides; polycarbonates and polyester-carbonates; polysulfones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-4
  • Polyamides and copolyamides which are derived from bisamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene bisamine and adipic acid; polyamides prepared from hexamethylene bisamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4 trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful.
  • copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers such as, for example, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols and polyamides or copolyamides modified with EPDM or ABS may be used.
  • Polyolefin, polyalkylene terephthalate, polyphenylene ether and styrenic resins, and mixtures thereof are more preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether homopolymers and copolymers, polystyrene, high impact polystyrene, polycarbonates and ABS-type graft copolymers and mixtures thereof being particularly preferred.
  • the present compositions may optionally contain a stabilizer or mixture of stabilizers, some for synergistic effects, in an amount ranging from about 50 ppm to about 5 wt. % of the total weight of the polymer resin composition.
  • the optional stabilizer additives are present in an amount of about 0.001 to about 2 wt. %.
  • the optional stabilizer additives are present in an amount of about 0.0025 to about 1 wt. %.
  • the optional stabilizers may be selected from the additive stabilizers of the prior art such as, for example, hindered phenols, hindered amines, and the like and mixtures thereof, may be optionally added to work in combination with and augment the stabilizers of the present invention.
  • the optional stabilizer or mixture of second stabilizers is selected from the group consisting of the phenolic antioxidants, hindered amine stabilizers, the ultraviolet light absorbers, organo-phosphorous compounds comprising of organo-phosphites and organo-phosphonites, alkaline metal salts of fatty acids, the hydrotalcites, metal oxides, epoxydized soybean oils, the hydroxyl amines, the tertiary amine oxides, thermal reaction products of tertiary amine oxides, and the thiosynergists, as further described below.
  • the second stabilizer additive may be an antioxidant such as, for example, alkylated mono-phenols, e.g., 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(.alpha-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6,-tricyclohexyphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, and the like; alkylated hydroquinones, e.g., 2,6-di-tert-butyl-4-methoxyphenol, 2,5-
  • antioxidants may also comprise hydroxylated thiodiphenyl ethers, non-limiting examples of which include 2,2′-thio-bis-(6-tert-butyl-4-methylphenol), 2,2′-thio-bis-(4-octylphenol), 4,4′-thio-bis-(6-tertbutyl-3-methylphenol), and 4,4′-thio-bis-(6-tert-butyl-2- methylphenol).
  • hydroxylated thiodiphenyl ethers non-limiting examples of which include 2,2′-thio-bis-(6-tert-butyl-4-methylphenol), 2,2′-thio-bis-(4-octylphenol), 4,4′-thio-bis-(6-tertbutyl-3-methylphenol), and 4,4′-thio-bis-(6-tert-butyl-2- methylphenol).
  • Alkylidene-bisphenols may be used as antioxidants.
  • examples include 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2′-methylene-bis-(6-tert-butyl4-ethylphenol), 2,2′-methylene-bis-(4-methyl-6-(.alpha- methylcyclohexyl)phenol), 2,2′-methylene-bis-(4-methyl-6-cyclohexyiphenol), 2,2′-methylene-bis-(6-nonyl-4-methylphenol), 2,2′-methylene-bis-(6-nonyl-4-methylphenol), 2,2′-methylene-bis-(6-(alpha-methylbenzyl)-4-nonylphenol), 2,2′-methylene-bis-(6-(.alpha,alpha-dimethylbenzyl)-4-nonyl-phenol).
  • the second stabilizer is a phenolic antioxidant selected from the group consisting of n-octadecyl, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl, tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane], di-n-octadecyl-3,5-di-tert-butyl4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-buty
  • the phenolic antioxidant is selected from the group consisting of octadecyl-3,5-di-tert-butyl-4-hydroxycinnamate, tetrakis[methylene(3,5-di-tert-butyl -4-hydroxyhydrocinnamate)]methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n- octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-p-cresol, and 2,2′- ethylidene-bis(4,6-di-tert-
  • the second antioxidant additive is a benzyl compound such as, for example, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl4-hydroxybenzyl-mercaptoacetate, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate. 1,3,5-tris-(3,5-di-tert-butyl-4,10-hydroxybenzyl)isocyanurate.
  • 1,3,5-tris-(3,5-di-tert-butyl-4,10-hydroxybenzyl) isocyanurate.
  • Acylaminophenols may be used as antioxidants.
  • antioxidants include, but are not limited to, 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, and octyl-N-(3,5-di-tert-butyl4-hydroxyphenyl)-carbamate.
  • Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)- propionic acid with monohydric or polyhydric alcohols as for example, methanol, ethanol, ethylene glycol, diethyleneglycol, triethyleneglycol, tridiethyleneglycol, neopentylglycol, 1,2-propanediol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, 3-thiaundecanol, 3-thiapentadecanol, pentaerythritol, tris-hydroxyethyl isocyanurate, trimethyldexanediol, trimethylolethane, trimethylolpropane, 4-hydroxylmethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, dihydroxyethyl oxalic acid diamide may also be used as antioxidants.
  • the second stabilizer additive is selected from one of UV absorbers and light stabilizers.
  • the ultraviolet light absorbers and light stabilizers may include 2H-benzotriazoles, benzophenones, oxanilides, alpha-cyanocinnamates, substituted benzoate esters, or nickel salts of the O-alkyl hindered phenolic benzylphosphonates.
  • UV absorbers and light stabilizers include the 2-(2′-hydroxyphenyl)-benzotriazoles, such as for example, the 5′-methyl-,3′5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl, 3′-sec-butyl-5′-tert-butyl-, 4′-octoxy, 3′,5′-ditert-amyl- and 3′,5′-bis-(alpha.
  • 2-(2′-hydroxyphenyl)-benzotriazoles such as for example, the 5′-methyl-,3′5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-,
  • Suitable 2-hydroxy-benzophenones such as for example, the 4-hydroxy-4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2′,4′-trihydroxy-, and 2′-hydroxy-4,4′-dimethoxy derivative may also be used as UV absorbers and light stabilizers.
  • UV absorbers and light stabilizers may also comprise esters of substituted and unsubstituted benzoic acids, such as for example, phenylsalicilate, (4-tertbutylphenyl)salicylate, (octylphenyl)salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,5-di-tert-butyl-4-hydroxybenzoic acid, 2,4-di-tert-butyl-phenyl- and 3,5-di-tert-butyl-4- hydroxybenzoate, and their—octadecyl ester, -2-methyl-4,6-di-tert-butyl-ester; and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
  • benzoic acids such as for example, phenylsalici
  • UV absorbers and light stabilizers include, but are not limited to, acrylates, e.g., alpha-cyano-beta-diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester, or butyl ester; alpha-carbomethoxy-p-methoxycinnamic acid methyl ester, and N-(beta-carbomethoxy-beta-cyanovinyl)-2-methyl-indoline.
  • acrylates e.g., alpha-cyano-beta-diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy cinnamic acid methyl ester, alpha-cyano-beta-methyl-p
  • the second stabilizer additive in the form of UV absorbers and light stabilizers may also comprise oxalic acid diamides, as for example, (4,4′-di-octyloxy)oxanilide, 2,2′-di-octyloxy-5′,5′-ditert-butyloxa nilide, 2,2′-di-dodecyloxy-5′,5′di-tert-butyl-oxanilide, 2-ethoxy-2′-ethyl-oxanilide; and N,N′-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2′-ethyloxanilide, and its mixture with 2-ethoxy-2′-ethyl-5,4-di-tert-butyloxanilide, and mixtures of ortho-and para-methoxy-as well as of o- and p-ethoxy-disubsti
  • UV absorbers and light stabilizers may comprise nickel compounds, as for example, nickel complexes of 2,2′-thio-bis(4-(1,1,1,3-tetramethylbutyl)-phenol), such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine, or N-cyclohexyl-diethanolamine; nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as the methyl, ethyl, and butyl esters; nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-penyl (pentyl or phenyl?) undecyl ketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.
  • nickel compounds as for example, nickel complexes of 2,2′-thio-bis(4
  • Sterically hindered amines may be used as UV absorbers and light stabilizers.
  • Examples include, but are not limited to, bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis5 (1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis(1,2,2,6,6,-pentamethylpiperidyl)ester, 4-benzoyl-2,2,6,6- tetramethylpiperidine, 4-stearyloxy-2,2-6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, di(1,2 ,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)- but
  • Amine oxides of hindered amine stabilizers are also included in the present invention. Condensation products of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, N,N′-(2,2,6,6-tetramethylpiperidyl)hexamethylendiamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6- tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-arbonic acid, and 1,1′(1,2- ethanediyl)-bis-(3,3,5 ,5-tetramethylpiperazinone); 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-
  • HALS Hindered Amines Light Stabilizers
  • HALS Hindered Amines Light Stabilizers
  • amines include, but are not limited to, butane tetracarboxylic acid 2,2,6,6-tetramethyl piperidinol esters.
  • Such amines include hydroxylamines derived from hindered amines, such as di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1-hydroxy 2,2,6,6-tetramethyl4-benzoxypiperidine; and 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di- tert-butyl-4-hydroxy hydrocinnamoyloxy)-piperdine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-epsilon-caprolactam.
  • the UV absorbers and light stabilizers may comprise hydroxyphenyl-s-triazines, as for example 2,6-bis-(2,4- dimethylphenyl)-4-(2-hydroxy-4octyloxyphenyl)-s-triazine, 2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 5 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis(2hydroxy-4- (2-hydroxyethoxy)phenyl)-6-phenyl-s-triazine; 2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)-phenyl)-6-(2,4-dimethylphenyl)-s-triazin
  • metal deactivators such as, for example, N,N′-diphenyloxalic acid diamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis-salicyloylhydrazine, N,N′-bis-(3,5-di-tert-butyl-4-hydrophenylpropionyl)-2-hydrazine, salicyloylamino-1,2,4-triazole, bis-benzyliden-oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidebeoxalic acid dihydrazide, N-salicylol-N′-salicylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N-bis-salicyloyl-thi
  • Phosphites and phosphonites such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl- phenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,4-di-cumylphenyl)pentaerythritol diphosphite and the like may be used in some embodiments of the presentation.
  • triphenyl phosphite dipheny
  • Peroxide scavengers such as, for example, the esters of beta-thiodipropionic acid such as, for example, the lauryl, stearyl, myristyl or tridecyl esters; mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyldithiocarbamate, dioctadecyldisulfide, and pentaerythritol tetrakis (beta-dodecylmercapto)propionate may also be used.
  • the esters of beta-thiodipropionic acid such as, for example, the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc-dibutyldithiocarbamate, dioctadecyldisulfide, and pen
  • the second stabilizer additive may be a hydroxylamine, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamnine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine, N,N-di-tert-butylhydroxylamine, N-cyclohexylhydroxylamine, N-cyclododecylhydroxylamine, N,N-dicyclohexylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-d
  • the second stabilizer additive is a nitrone, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-.alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-penta
  • the optional second stabilizer additive is a polyamide stabilizer such as for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers and neutralizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, and polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, e.g., calcium stearate, calcium stearoyl lactate, calcium lactate, zinc stearate, magnesium stearate, sodium ricinoleate, and potassium palmitate; antimony pyrocatecholate, zinc pyrocatecholate, and hydrotalcites and synthetic hydrotalcites, may also be used.
  • hydroxy carbonates, magnesium zinc hydroxycarbonates, magnesium aluminum hydroxycarbonates, and aluminum zinc hydroxycarbonates; as well as metal oxides, e.g., zinc oxide, magnesium oxide and calcium oxide may also be used.
  • Nucleating agents may also be used herein. Suitable nucleating agents include, but are not limited to, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium salt of methylene bis-2,4-dibutylphenyl, cyclic phosphite esters, sorbitol tris-benzaldehyde acetal, and sodium salt of bis(2,4-di-t-butylphenyl) phosphite, sodium salt of ethylidene bis(2,4-di-t-butyl phenyl)phosphite and the like and combinations thereof.
  • the optional (i.e., the second) additives and stabilizers described herein are present in an amount effective to further improve the composition stability.
  • the stabilizer combinations may be incorporated into the polymer resins by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
  • optional additives other than those described hereinabove may be included, e.g., fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
  • fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
  • additives such as, for example, plasticizers; epoxidized vegetable oils, e.g., epoxidized soybean oils; lubricants, e.g., stearyl alcohol; emulsifiers, pigments, optical brighteners, flame proofing agents, anti-static agents, blowing agents, anti-blocking agents, clarifiers, anti-ozonants, optical brighteners, flame-proofing agents, and thiosynergists such as, for example, dilaurythiodipropionate, distearylthiodipropionate, neopentanetetrayl, and tetrakis(3-dodecylthioproprionate).
  • plasticizers e.g., epoxidized soybean oils
  • lubricants e.g., stearyl alcohol
  • emulsifiers pigments, optical brighteners, flame proofing agents, anti-static agents, blowing agents, anti-blocking agents, clar
  • the stabilizers of this invention advantageously assist with the stabilization of polymer resin compositions especially in high temperature processing against changes in melt index and/or color, even though the polymer resin may undergo a number of extrusions.
  • the stabilizers of the present invention may readily be incorporated into the resin compositions by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
  • the stabilizer may be mixed with the resin in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
  • the polymer resin compositions of the present invention can be prepared by a variety of methods, e.g., intimate admixing of the ingredients with any additional materials desired in the formulation. Suitable procedures include solution blending and melt blending. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. Examples of equipment used in such melt compounding methods include: co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment.
  • ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other or with a portion of the polymer resin to make a stabilizer concentrate.
  • certain additives may be pre-compounded with each other or with a portion of the polymer resin to make a stabilizer concentrate.
  • Those of ordinary skill in the art will be able to adjust blending times and temperatures, as well as component addition, location and sequence, without undue additional experimentation.
  • the stabilizers of this invention may be conveniently incorporated by conventional techniques into polymer resins before the fabrication thereof into shaped articles, it is also possible to apply the instant stabilizers by a topical application to the finished articles.
  • Articles comprising the phosphite stabilizer compounds of the present invention may be made by, for example, extrusion, injection molding, blow molding, rotomolding, or compaction.
  • All of the stabilizer ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other or with a portion of the polymeric resin to make a stabilizer concentrate.
  • the additives including the phosphite stabilizer of the invention may be incorporated into the resins by conventional techniques, and at any convenient stage prior to the manufacture of shaped articles.
  • the stabilizer may be mixed with the resin in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
  • the stabilizer is applied as a topical application to the finished articles, e.g., fiber articles, for example, by way of a spin finish during the melt spinning process.
  • compositions of the present invention can be prepared by a variety of methods, e.g., intimate admixing of the ingredients with any additional materials desired in the formulation, e.g., solution blending, melt blending, melt compounding, etc., using a variety of equipment and methods including co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment.
  • the neoalkyl chlorophosphite is prepared.
  • Reaction equipment including 1 liter, 4-necked reaction vessel equipped with a stirring apparatus, reflux column, distillation head, condenser, temperature probe, and dropping funnel, is cleaned and moisture is removed by heating and reducing the pressure on the system.
  • a total of 261.22 grams (1.63 moles) of 2-butyl-2-ethyl-1,3-propanediol and 500 grams of dry heptane is placed into the reaction vessel.
  • a sweeping of dry inert gas is passed through a scrubber to remove hydrogen chloride gas generated during the reaction.
  • the reaction flask is cooled to approximately 5° C. using a wet ice bath.
  • reaction mixture After addition of the phosphorus trichloride is complete, the reaction mixture is allowed to slowly warm to room temperature. The reaction mixture is distilled to a pot temperature of about 165° C. at atmospheric pressure to remove any heptane and excess phosphorus trichloride. The reaction mixture is cooled to approximately 35° C. and vacuum applied. The fraction is collected in distillation at a head temperature of 139-140° C. at a pressure of 16 torr, for a yield of about 92% of (2-butyl-2-Ethyl-1,3-propanediol) chlorophosphite.
  • 2-butyl-2-ethyl-1,3-propanediol chlorophosphite is prepared by reacting molten 2-butyl-2-ethyl-1,3-propanediol with PCl 3 at less than 5° C., held for 24 under inert atmosphere (N 2 ), subsequently followed with the removal of HCl gas and then isolating the product for (2-butyl-2-ethyl-1,3-propanediol) chlorophosphite of high purity (98+%) in high yields ( ⁇ 95%).
  • 2,4-di-t-butylphenol is added to the reaction vessel capable of withstanding approximately 2 torr of pressure, equipped with a stirring apparatus, reflux column, distillation head, temperature probe, and a vacuum pump capable of pulling 2-3 torr of vacuum.
  • the pressure is reduced to 20 torr and held for 1 hour to remove residual water from the raw material.
  • the molten material is cooled to approximately 60° C. and the pressure in the vessel is raised to 100 torr. Exit gas is passed through a scrubber to remove any generated hydrogen chloride gas.
  • 2-butyl-2-ethyl-1,3-propanediol monochlorphosphite is slowly charged to the reaction vessel at 60° C.
  • the pressure is reduced to about 50-70 torr and the temperature is held in the range of about 60-77° C. for about 2-4 hours.
  • the vacuum is broken under dry inert gas and 1 mole % of a catalyst relative to the loading of the 2-butyl-2-ethyl-1,3-propanediol monochlorphosphite is added.
  • the reaction vessel pressure is reduced to 50 torr and the reaction temperature is held at 75-77° C. for a period of 6 hours.
  • the reaction temperature is increased to 83-85° C. at 50 torr and held for a period of 12 hours.
  • the reactant feed 2-butyl-2-ethyl-1,3-propanediol monochlorphosphite is less than 1.5% by GC (Gas Chromatographic analysis), the temperature is slowly increased to 150° C.
  • the pressure is then slowly reduced to 2-3 torr and the phosphite product is hard stripped to terminal conditions of 220° C reaction mixture temperature and a head temperature of greater than about185° C.
  • the final product 2,4-di-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite (Phosphite-1) is viscous liquid with purity level of 95% or greater (via GC) and with a reaction yield of about 94.61%.
  • Example 3 is repeated except that HCl is removed by a sweep of nitrogen gas above the surface of the reaction contents, for similar results in terms of product yield and purity level.
  • a neopentylglycol chlorophosphite is first prepared with the reaction of 67.7 g of neopentyl glycol in 300 mL of methylene chloride and 111.6 g of phosphorus trichloride in a process as described in Example 1.
  • the product is vacuum distilled at 80° C. at 18 mm of Hg, for 104.2 g of colorless neopentylglycol chlorophosphite and a yield of 95%.
  • the stabilizers of the present invention as prepared above and comparable/prior art phosphite stabilizers are compounded into a polypropylene resin, e.g., a commercially available resin from Basell under the tradename of Profax R6301.
  • resin composition is blended/mixed using Turbula Blender for 30 minutes.
  • the stabilizer used, if liquid, is pre-blended with a portion of a resin, which is then subsequently blended with the resin and mixed well using Turbula Blender.
  • the formulation is extruded at 100 rpm from 1 inch (2.54 cm) diameter Killion extruder at 500° F. (260° C). The rpm and temperatures may be adjusted according to the resin utilized.
  • resin pellets are compression molded into 125 mil (3.2 mm) thick plaques at 370° F. (188° C.).
  • Phenol-1 Octadecyl 3,5-di(tert)-butyl-4-hydroxyhydrocinnamate, a commercially available hindered phenol form Ciba Specialty Chemicals under trade name Irganox 1076.
  • Phenol-2 Tetrakis (methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionatemethane, a commercially available hindered phenol from Ciba Specialty Chemicals under trade name Irganox 1010.
  • Phosphite-1 2,4-Di-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite.
  • Phosphite-2 2,4,6-Tri-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite, a commercially available phosphite from GE Specialty Chemicals under the trade name ULTRANOX 641.
  • Phosphite-3 Tris(2,4-di-tert-butyl-phenyl)phosphite, a commercially available phosphite from Ciba Specialty Chemicals under trade name Irgafos 168.
  • Phosphite-4 Tris(nonylphenyl)phosphite with tri-isopropanolamine from GE Specialty Chemicals under trade name WESTON-399.
  • Phosphite-5 Tri-lauryl phosphite from GE Specialty Chemicals.
  • ZnO Zinc Oxide
  • CaSt Calcium Stearate.
  • Example 7 is a composition comprising Profax R6301, 500 ppm of calcium stearate, and 500 ppm of 2,4-di-tert-butylphenyl (2-butyl-2-ethyl-1,3-propanediol)phosphite (Phosphite-1) of the present invention.
  • Comparative Example 1 contains 2,4,6-tri-tert-butylphenyl (2-butyl-2-ethyl-1,3-propanediol)phosphite (Phosphite-2), a commercially available phosphite in the prior art.
  • the specimen samples are measured for yellowness index (YI) with a low YI value indicates less yellowing.
  • the melt flow rate (in grams/10 minutes) per ASTM-D-1238 is also measured on the pellets after the first, third and fifth extrusions. The closer the melt flow rate after the fifth extrusion is to the melt flow rate after the first extrusion indicates the improved/desirable process stabilization.
  • the performance of the phosphite stabilizer (Phosphite-1) of the present invention is comparable to the Phosphite-2 of the prior art, but with an improvement in handling of the product with an advantage of the odor level being low to none.
  • Examples 8 and 9 of Table 2 are compositions comprising Profax R6301, 500 ppm of calcium stearate, and 500 ppm of the phosphite of the present invention (Phosphite-1 above).
  • Comparative Example 2 comprises Profax R6301, 500 ppm of calcium stearate and 500 ppm of phenol 2. Examples 8 and 9 gave superior color in polypropylene under the extrusion conditions as compared to Comparative Example 2. TABLE 2 Ex./Comp. Ex. Ex. 8 Ex. 9 Comp. Ex.
  • the resin comprising the stabilizers is blended for 30 minutes using a Turbula Blender.
  • the stabilized resin formulation is extruded in a Killion extruder at 100 rpm from 1 inch (2.54 cm) diameter opening at 230° C.
  • the resin pellets are compression molded into 125 mil (3.2 mm) thick plaques at 188° C.
  • Specimen yellowness index (YI) and MFR (in grams/10 minutes) per ASTM-D-1238 190° C./2.16 Kg, 190° C./21.6 Kg, and referred to as I-2 and I-21 respectively in Table 3 are determined on the pellets after the first, third and fifth extrusions.
  • Examples have 200 ppm of ZnO and 500 ppm of phenol-1 and respective phosphite additive as set forth in Table-3.
  • the data is set forth below in Table 3.
  • the data tabulated in examples 1-6 are on equal loading level of phosphites-1, phosphite-2, phosphite-3, phosphite4, and phosphite-5.
  • Examples 10 and 11 containing the phosphite of the present invention give well balanced performance by holding the molecular weight of the polymer (LLDPE) and color well.
  • a polyethylene is used as the base polymer resin, i.e., a Ziegler catalyzed LLDPE.
  • Comparative Example 9 is the comparative example comprising an unstabilized linear low density polyethylene (Ziegler catalyzed LLDPE) and 500 ppm of Phenol-1, a phenol stabilizer in the prior art.
  • Examples 12 and 13 are the examples of the invention, with 500 ppm of Phenol-1.
  • Phosphite-1 gives a well balanced properties in LLDPE resin at 1500 ppm loading level compared to Comparative Examples 3, 4, 5 and 6 of the prior art.
  • the phosphite of the present invention Phosphite-1 is comparable to the phosphite of the prior art, Phosphite-2.
  • viscosity of Phosphite-1 composition (neat) comprising the phosphite of the invention is compared to a composition known in the prior art, Phosphite-4. Viscosities are measured using the Cannon-Fenske Routine Viscometer (ASTM D 445/D 2515).
  • Comparative Example 12 of about 50 g of Phosphite-1 as prepared by amine acceptor route (Phosphite A), and not containing tri-isopropanolamine, and Example 12, another Phosphite-1, as prepared by a direct route (Phosphite B) and not containing tri-isopropanolamine, were placed in a 4 oz. wide mouth bottle at room temperature. A panel of five evaluators were asked for an odor evaluation of the product by opening the cap and breathing the air-space above the phosphites carefully. All the panelists indicated that Comparative Example 12 containing Phosphite A (prepared by amine acceptor route, and not containing tri-isopropanolamine) has a slight amine like odor. The panelists also rated Example 16 containing Phosphite B (prepared by a direct route and not containing tri-isopropanolamine) to be odorless or has almost no odor compared to Comparative Example 12.
  • a chromium catalyzed high density polyethylene resin (Cr-HDPE) used as the base polymer resin 1060 ppm of 2,4-di-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite prepared in accordance with the procedure set forth in Example 3 above was added together with 1000 ppm IrganoxTM 1010, 2000 ppm calcium stearate and 1000 ppm zinc stearate to provide a stabilized polymer.
  • the Cr-HDPE comprising the stabilizers of Example 17 and Comparative Examples 13 and 14 were compounded at 230° C. under an inert atmosphere and extruded five times on a 1′′ Killion extruder at 230° C. under air.
  • the melt flow was measured on the 1 st , 3 rd , and 5 th pass according to ASTM method D1238-86. Color measurements were made on 3.18 mm compression molded plaques according to ASTM method D1925-70. Gas-fade testing was carried out using AATCC test method 164-1987 at 60° C.
  • the Cr-HDPE sample of Example 17 using the phosphite within the scope of the present invention had an excellent hydrocarbon solubility, improved hydrolytic stability, high polymer compatibility, and excellent activity for melt and color stabilization at low levels, resulting in cost effective formulations as compared to the Cr-HDPE sample of Comparative Examples 13 and 14 using phosphites outside the scope of the invention.
  • FIGS. 1 and 2 show the melt flow control and color, respectively, observed with the Cr-HDPE sample of Example 17 using a phosphite within the scope of the present invention as compared to the Cr-HDPE sample of Comparative Examples 13 and 14 using phosphites outside the scope of the invention. All three phosphites exhibited comparable molecular weight protection during multipass extrusion at 230° C. Clearly, the sample of Example 17 using a phosphite within the scope of the present invention gave better color than both samples of Comparative Examples 13 and 14.
  • the ZN-LLDPE comprising the stabilizers of Example 18 and Comparative Examples 15 and 16 were compounded at 230° C. under an inert atmosphere and extruded five times on a 1′′ Killion extruder at 230° C. under air.
  • the melt flow was measured on the 1 st , 3 rd , and 5 th pass according to ASTM method D1238-86. Color measurements were made on 3.18 mm compression molded plaques according to ASTM method D1925-70. Gas-fade testing was carried out using AATCC test method 164-1987 at 60° C.
  • FIGS. 5 and 6 show the melt flow control and color, respectively, observed with the ZN-LLDPE sample of Example 18 using a phosphite within the scope of the present invention as compared to the ZN-LLDPE sample of Comparative Examples 15 and 16 using phosphites outside the scope of the invention.
  • the ZN-LLDPE sample of Example 18 using a phosphite within the scope of the present invention showed comparable performance as a melt flow stabilizer at one half the dosing level compared to the ZN-LLDPE samples of Comparative Examples 15 and 16 using a phosphite outside the scope of the invention.
  • the ZN-LLDPE sample of Example 18 exhibited superior color retention, using half the loading level of the phosphite, during multipass extrusion as compared ZN-LLDPE samples of Comparative Examples 15 and 16 using a phosphite outside the scope of the invention ( FIG. 7 ) when exposed to NOx gases. Therefore, the ZN-LLDPE sample of Example 18 provided better gas fading resistance compared to the ZN-LLDPE samples of Comparative Examples 15 and 16.
  • m-LLDPE metallocene-catalyzed linear low density polyethylene resin
  • base polymer resin 750 ppm of 2,4-di-tert-butylphenyl(2-butyl-2-ethyl-1 ,3-propanediol)phosphite prepared in accordance with the procedure set forth in Example 3 above was added together with 500 ppm of Irganox 1076 to provide a stabilized polymer.
  • the m-LLDPE comprising the stabilizers of Example 19 and Comparative Examples 17 and 18 were compounded at 230° C. under an inert atmosphere and extruded five times on a 1′′ Killion extruder at 230° C. under air.
  • the melt flow was measured on the 1 st , 3rd, and 5 th pass according to ASTM method D1238-86. Color measurements were made on 3.18 mm compression molded plaques according to ASTM method D1925-70. Gas-fade testing was carried out using AATCC test method 164-1987 at 60° C.
  • the m-LLDPE sample of Example 19 using the phosphite within the scope of the present invention had an excellent hydrocarbon solubility, improved hydrolytic stability, high polymer compatibility, and excellent activity for melt and color stabilization at low levels, resulting in cost effective formulations as compared to the m-LLDPE sample of Comparative Examples 17 and 18 using phosphites outside the scope of the invention.
  • FIGS. 8 and 9 show the melt flow control and color, respectively, observed with the m-LLDPE sample of Example 19 using a phosphite within the scope of the present invention as compared to the m-LLDPE sample of Comparative Examples 17 and 18 using phosphites outside the scope of the invention. All three phosphites exhibited comparable molecular weight protection during multipass extrusion at 230° C. Clearly, the sample of Example 19 using a phosphite within the scope of the present invention gave better color than both samples of Comparative Examples 17 and 18, at half the dosing level.
  • Example 19 provided the best balance of stabilization and color during extrusion, storage, and gas fading conditions at half the dosing levels compared to the m-LLDPE samples of Comparative Examples 17 and 18.
  • Polymer performance evaluation employing a phosphite within the scope of the invention demonstrated a better balance of properties and exhibited improved performance attributes in a wide range of polyolefins, such as Cr-HDPE, ZN-LLDPE, and m-LLDPE.
  • polyolefins such as Cr-HDPE, ZN-LLDPE, and m-LLDPE.
  • the phosphite of the present invention showed superior color retention when the polymer samples were exposed to NOx gases. That is, optimal performance for a given application can be achieved with this tailor-made liquid phosphite for better performance, less discoloration during processing, NOx exposure, and thermal aging.
  • the phosphite of the present invention possessed an excellent balance of properties and performance in the polyolefins at half the dosing level compared to the phosphites outside the scope of the invention.
  • the propylene homopolymer comprising the stabilizers of Example 20 and Comparative Examples 19 and 20 were compounded at 230° C. under an inert atmosphere and extruded five times on a 1′′ Killion extruder at 230° C. under air.
  • the melt flow was measured on the 1 st , 3 rd , 5 th pass according to ASTM method D1238-86. Color measurements were made on 3.18 mm compression molded plaques according to ASTM method D1925-70.
  • FIGS. 11 and 12 show the melt flow control and color, respectively, observed with the m-LLDPE sample of Example 20 using a phosphite within the scope of the present invention as compared to the m-LLDPE sample of Comparative Examples 19 and 20 using phosphites outside the scope of the invention. All three phosphites exhibited comparable molecular weight protection during multipass extrusion at 230° C. The sample of Example 20 using a phosphite within the scope of the present invention gave better color than both samples of Comparative Examples 19 and 20.
  • Polypropylene samples (Profax 6301) were compounded on a 1′′ Killion extruder at 230° C. under inert atmosphere using the following components: (1) 2,4-di-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite prepared in accordance with the procedure set forth in Example 3 above; (2) 2,4-di-tert-butylphenyl-1 which is the hydrolysis product of the 2,4-di-tert-butylphenyl(2-butyl-2-ethyl-1,3-propanediol)phosphite prepared in accordance with the procedure set forth in Example 3 above, (3) 2,4-di-tert-butylphenyl-2 which is the hydrolysis product of tris(2,4-di-tert-butylphenyl)phosphite, (4) nonylphenol and (5) tris(nonylphenyl)phosphit

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US20070105992A1 (en) * 2005-11-07 2007-05-10 Hayder Zahalka Cycloalkyl phosphites as stabilizers for thermoplastic resins
US20100076129A1 (en) * 2008-09-24 2010-03-25 Hayder Zahalka Blended phosphite or phosphonite compositions having improved hydrolytic stability
US20100143630A1 (en) * 2008-01-16 2010-06-10 The Yokohama Rubber Co., Ltd. Chlorinated rubber composition and hose
WO2014074596A1 (fr) * 2012-11-08 2014-05-15 Equistar Chemicals, Lp Composition de polyéthylène haute densité stabilisé ayant une résistance améliorée à la dégradation et système de stabilisant
US20160032078A1 (en) * 2013-03-15 2016-02-04 Baerlocher Gmbh Stabilized polymer compositions and methods of making same
US9273266B2 (en) 2010-09-24 2016-03-01 Dow Global Technologies Llc Non-aromatic based antioxidants for lubricants
CN111116984A (zh) * 2019-12-31 2020-05-08 山东振曦新材料科技有限公司 一种液体氯化石蜡高效复合稳定剂及其制备方法
US10995214B2 (en) * 2016-10-31 2021-05-04 Lg Chem, Ltd. Polycarbonate resin composition and optical molded article using the same
CN115819842A (zh) * 2023-01-09 2023-03-21 中化泉州石化有限公司 一种聚合物用的含受阻酚的耐着色抗氧剂组合物

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JP2007009078A (ja) * 2005-06-30 2007-01-18 Fujifilm Holdings Corp ポリオレフィン樹脂組成物及びそのゲル発生抑制方法、並びに画像記録材料用支持体及びその製造方法
EP2634211B1 (fr) * 2011-12-16 2015-07-15 Solvay Specialty Polymers USA, LLC. Composition de polymère résistant à la lumière et à la chaleur
CN110204789B (zh) * 2019-06-24 2021-03-19 东莞市尚诺新材料有限公司 一种透明管材用稳定剂及其制备方法

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WO2014074596A1 (fr) * 2012-11-08 2014-05-15 Equistar Chemicals, Lp Composition de polyéthylène haute densité stabilisé ayant une résistance améliorée à la dégradation et système de stabilisant
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US10995214B2 (en) * 2016-10-31 2021-05-04 Lg Chem, Ltd. Polycarbonate resin composition and optical molded article using the same
CN111116984A (zh) * 2019-12-31 2020-05-08 山东振曦新材料科技有限公司 一种液体氯化石蜡高效复合稳定剂及其制备方法
CN115819842A (zh) * 2023-01-09 2023-03-21 中化泉州石化有限公司 一种聚合物用的含受阻酚的耐着色抗氧剂组合物

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